Organic peroxides obtained by reaction of hydroperoxides with hydroxy- acetone and process



United States Patent ORGANIC PEROXIDES OBTAINED BY REACTION OFHYDROPEROXIDES WITH HYDROXY- ACE- TONE AND PROCESS Yun G. Chang, Austin,Tex., assignor to Reichhold Chemicals, Inc., White Plaines, N.Y. NoDrawing. Filed Jan. 19, 1968, Ser. No. 699,064 Int. Cl. C07d 15/10; C08f1/60 US. Cl. 260340.6 11 Claims ABSTRACT OF THE DISCLOSURE Thisinvention discloses a novel class of peroxides having the followingformula:

l/K ROOC CH2 H2O CO-OR wherein R is a hydrogen atom, an alkyl group, anaralkyl group, an acyl or aracyl group and the method of preparing sameby reacting hydroxy-acetone with hydroperoxide at a temperature of 0 C.to 80 C. in the presence of an acidic catalyst.

The invention relates to peroxides having the following formula:

wherein R is a hydrogen atom, an alkyl group, an aralkyl group, an acylor aracyl group and the method of preparing same by reactinghydroxy-acetone with hydroperoxides at a temperature of 0 C. to 80 C. inthe presence of an acidic cataylst.

It is an object of this invention to provide a novel class of peroxideswhich are highly efiicient polymerization initiators.

It is another object of this invention to provide highly efficientmethods for the preparation of such polymerization initiators.

It is still another object of this invention to produce these peroxidesfrom hydroxy-acetone.

These and other objects and advantages of the present invention willbecome more apparent from the detailed description thereof set forthhereinbelow.

It has now been found that these objectives can be attained by reactinghydroxy-acetone with hydroperoxides in the presence of an acidiccatalyst. This reaction takes place at a temperature ranging from about0 C. to 80 C.

The preferred temperature however is between about 0 C. and C., onaccount of the outstanding results obtained therefrom.

In the reaction of this invention, the mol ratio of hydroxy-acetone tohydroperoxide may vary widely, from 10:1 to 1:10. However, thepreferable rnol ratio of hydroxyacetone to hydroperoxide is in the rangeof 2:1 to 1:1. It has been found that the use of a large excess ofhydroperoxide for the reaction causes more. side reactions, andconsequently, the formation of more byproducts.

The hydroperoxide used in this invention is represented by the formula:

wherein R can be either a hydrogen, an alkyl group, an aralkyl group, anacyl group or an aracyl group. The preferred hydroperoxides would be thehydroperoxides,

3,480,648 Patented Nov. 25, 1969 In order to understand the mechanism ofthe reaction the following equation is exemplified:

wherein R is a hydrogen atom, an alkyl group, an aralkyl group, an acylgroup or an aracyl group.

This novel class of organic peroxides has been found to provide goodcatalysts or initiators in polymerization reactions, such as thepolymerization of styrene, vinyl acetate, alkyl methacrylates, and thelike. They have also been found to be useful as cross-linking agents.

EXAMPLE I Preparation of 2,5-di-t butylperoxy-2,5-dimethyl- 1,4-dioxaneTwo hundred and thirty-four grams (3.0 moles) of 95% hydroxy acetone wasmixed with 70. 0 g. (0.5 mole) of 70% sulfuric acid in a beaker, at roomtemperature, with stirring. To the resulting mixture was slowly added300.0 g. (3.0 moles) of t-butyl hydroperoxide, at 0 C., with powerfulagitation. The reaction mixture was stirred at from 0 C. to 10 C. for anhour. The colorless crystalline solid product was filtered off andWashed four times with water in the funnel. Then, it was sucked todryness. The crude product weighed 353.0 g., indicating a 40.5% yieldbased upon the hydroxy-acetone used for the reaction. It melted at 66 C.and contained 12.61% active oxygen determined by hydriodic acid-sodiumthiosulfate titration and 7.14% active oxygen shown by the potassiumiodide-sodium thiosulfate titration.

.The product was purified by five crystallizations from dilute ethylalcohol. The pure material melted at 92 C. and contained 11.15% and2.48% active oxygen determined by the treatment with hydriodic acidsolution and by the treatment with potassium iodide solution,respectively, compared with the theoretic active oxygen content 10.96%.

Analysis.--Calcd. for C H O C, 57.51; H, 9.65; O, 32.84. Molecularweight 292.4. Found: C, 57.33 H, 9.74; O, 32.98. Molecular weight 297.

The infrared spectrum of this compound showed a strong band at 2950 cm.due to CH and CH groups, a strong band at 1365 cmr due to a C (CH group,very strong bands at 1190 cmr 1140 cmf and 1085 cmr indicating thestructure of p-dioxane, and a very strong band at 865-870 cm.-representing peroxide groups.

On the basis of these data, the structural formula of this new peroxideis assigned as below.

Preparation of 2,5-di-t-amylperoxy- 2,5-dimethyll,4dioxane To a mixtureof 7.8 g. (0.1 mole) of 95% hydroxyacetone and 2.4 g. (0.017 mole) of70% sulfuric acid, in a beaker, was slowly added 10.4 g. (0.1 mole) oftamyl hydroperoxide, at C., with powerful agitation. The reactionmixture was stirred at 010 C. for an hour. A colorless crystalline solidproduct was obtained in about 40% yield based on the amount ofhydroxy-acetone used for the reaction. This compound was the peroxide2,5-di-t-amylperoxy 2,5 dimethyl 1,4 dioxane, as shown by thedetermination of its active oxygen content.

EXAMPLE III Preparation of 2,5-dicumylperoxy-2,5- dimethyl-1,4-dioxaneTo a mixture of 7.8 g. (0.1 mole) of 95% hydroxyacetone and 2.4 g.(0.017 mole) of 70% sulfuric acid, in a beaker was slowly added 15.2 g.(0.1 mole) of cumyl hydroperoxide at 0 C., with powerful agitation. Thereaction mixture was stirred at 010 C. for an hour. A colorlesscrystalline solid product was obtained in about 40% yield based upon thequantity of hydroxy-acetone used for the reaction. As indicated by theactive oxygen content, this new peroxide was 2,5-dicurnylperoxy 2,5-dimethyl-1,4-dioxane.

What is claimed is:

1. A process of preparing an organic peroxide comprising reacting (1)hydroxy-acetone at a temperature of from about 0 C. to about 80 C. inthe presence of an acidic catalyst selected from a group consisting ofsulfuric acid, hydrochloric acid, perchloric acid and phosphoric acid,with (2) a hydroperoxide having the formula wherein R is a member of thegroup consisting of butyl, amyl and cumyl, said hydroxy-acetone and saidhydroperoxide reacting at mole ratios of from about 10:1 to about 1:10.

2. A process according to claim 1 wherein the temperature of thereaction is between about 0 and about 10 C.

3. A process according to claim 1 wherein the amount of the acidiccatalyst used ranges from about 10% to about 15% based on the weight ofthe reaction mixture.

4. A process according to claim 1 wherein the acidic catalyst used issulfuric acid having a strength of about 5. A process according to claim1 wherein the hydroperoxide is tertiary butyl hydroperoxide.

6. A process according to claim 1 wherein the hydroperoxide is tertiaryamyl hydroperoxide.

7. A process according to claim 1 wherein the hydroperoxide is cumylhydroperoxide.

8. An organic peroxide having the formula:

HsC O wherein R is a member of the group consisting of butyl, amyl andcumyl.

9. 2,5-di-t-buty1peroxy-2,5dimethy1-1,4-dioxane. 10.2,5,di-t-amylperoxy-2,5-dimethyl-1,4-dioxane. 11.2,5-dicurnylperoxy-Z,S-dimethyl-1,4-dioxane.

References Cited UNITED STATES PATENTS 3,149,126 9/1964 Milas 260340.6 X

ALEX MAZEL, Primary Examiner JAMES H. TURNIPSEED, Assistant Examiner

